EP0129211A1 - 2,6-Trans-dimethyl morpholine derivatives, fungicides containing them and methods of combating fungi - Google Patents

2,6-Trans-dimethyl morpholine derivatives, fungicides containing them and methods of combating fungi Download PDF

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Publication number
EP0129211A1
EP0129211A1 EP84106796A EP84106796A EP0129211A1 EP 0129211 A1 EP0129211 A1 EP 0129211A1 EP 84106796 A EP84106796 A EP 84106796A EP 84106796 A EP84106796 A EP 84106796A EP 0129211 A1 EP0129211 A1 EP 0129211A1
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Prior art keywords
trans
dimethyl
morpholine
compound
formula
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German (de)
French (fr)
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EP0129211B1 (en
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Ernst Dr. Buschmann
Karl-Heinz Dr. Koenig
Ernst-Heinrich Dr. Pommer
Nikolaus Dr. Drescher
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C07D295/033—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to carbocyclic rings

Definitions

  • the present invention relates to 2,6-trans-dimethylmorpholine derivatives, fungicides containing them and methods for combating fungi.
  • N-substituted 2,6-dimethylmorpholines in particular tridecyl-2,6-dimethylmorpholine (tridemorph) as fungicides.
  • tridecyl-2,6-dimethylmorpholine tridemorph
  • the known active ingredients consist of mixtures of the derivatives of 2,6-cis and 2,6-trans-dimethylmorpholine. The plant tolerance of these substances is in many cases not sufficient.
  • 2,6-trans-dimethylmorpholine derivatives of the formula in which R represents a cycloalkyl, cycloalkylalkyl or alkyl radical, which can be substituted by one or more C I -C 7 alkyl radicals, and the total number of carbon atoms of the substituent R is 7 to 20 and its N-Dxide and plant-compatible acid addition salts and metal complexes are much better tolerated by plants than the corresponding 2,6-cis-dimethylmorpholine derivatives.
  • the new 2,6-transdimethylmorpholine compounds are better tolerated by plants than the corresponding known cis / trans mixtures (tridemorph).
  • R means, for example, n-nonyl, n-decyl, n-tridecyl, n-dodecyl, nC 14 H 29 , nC 15 H 31 , nC 20H411 1,5,9-trimethyldecyl, 3,7,11-trimethyldodecyl, 3-ethyl -1,3,7-trimethyl-octyl, 2-methyl-tridecyl, 3,5,5-trimethylhexyl, 4-ethyl-1-methyl-octyl, 1,4-diethyl-octyl, 2-hexyl-hexyl, 1 -Methyl - dodecyl, 2-methyldodecyl, 2-ethyl-5-cyclohexylpentyl, cyclododecylmethyl, 4-ethyl-1-isobutyl-octyl, cyclooctyl, cyclonon
  • N-oxides are, for example, Nn-tridecyl-2,6-trans-dimethylmorpholine- N- oxide, N-cyclododecyl-2,6-tranodimethylmorpholine-N-oxide, a mixture consisting of N-alkyl-2,6-trans -dimethylmorpholln-N-oxides, the alkyl radical containing 11 to 14 carbons.
  • Acid addition salts are, for example, the salts with hydrochloric acid, HBr, H Z S0 4 , H 3 P0 4 , acetic acid, propionic acid, oxalic acid, n-dodecylsulfonic acid, n-dodecylphenylsulfonic acid.
  • Metal complexes are e.g. the complexes with copper, magnesium, zinc.
  • the aliphatic or cycloaliphatic radicals R can contain asymmetric carbons.
  • the active compounds of the formula I can therefore be present in the form of various enantiomers or diastereomers.
  • the pure enantiomers and diastereomers and their mixtures are encompassed by this invention.
  • isotridecanol (with isotridecanol we refer to a commercially available mixture of different homologous C 11 -C 14 alcohols which contains 60 to 70% tridecyl alcohol) were added dropwise to 322 g SOC1 2 . The mixture was stirred overnight, heated to 140 ° C. for 2 h, the crude product was distilled and 433 g of colorless oil were obtained, bp 84 to 86 ° C./0.3 bar.
  • the enamine (B) obtained was dissolved in ethyl acetate and, after the addition of 5 g of Pd / C contact (10% by weight of Pd), was hydrogenated at 60 to 70 ° C./100 bar. Then it was concentrated and distilled. 45 g of colorless oil, b.p. 136 to 138 ° C / 0.2 mbar were obtained.
  • the new compounds and their salts, metal complex compounds and oxides are distinguished by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes and Basidiomycetes. Some of them are systemically effective and can be used as foliar and soil fungicides. They can also be used in material protection.
  • the fungicidal compounds are particularly interesting for controlling a large number of fungi on various crop plants or their seeds, in particular wheat, rye, barley, oats, rice, corn, cotton, soybeans, coffee, bananas, sugar cane, fruit and ornamental plants in horticulture, and Vegetables - such as cucumbers, beans and pumpkin plants -.
  • the compounds are applied by spraying or dusting the plants with the active compounds or by treating the seeds of the plants with the active compounds. It is used before or after the plants or seeds are infected by the fungi.
  • the new substances can be converted into the usual formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the application forms depend entirely on the purposes; in any case, they should ensure a fine and uniform distribution of the active substance.
  • the formulations are prepared in a known manner, for example by extending the active ingredient with solvents and / or carriers, if appropriate using emulsifiers and dispersants, and if water is used as the diluent, other organic solvents can also be used as auxiliary solvents.
  • auxiliaries solvents such as aromatics (eg xylene, benzene), chlorinated aromatics (eg chlorobenzenes), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol), amines (eg ethanolamine, dimethylformamide) and water; Carriers such as natural stone powder, for example kaolins, clays, talc, chalk and synthetic stone powder (for example highly disperse silica, silicates); Emulsifiers, such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ether, Alkyl sulfonates and aryl sulfonates) and dispersants such as lignin, sulfite waste liquors and methyl cellulose.
  • solvents such as aromatics (eg xylene, benzene), chlorinated aromatics (eg chlorobenzenes), paraffins (eg petroleum fractions), alcohols (eg methanol, but
  • the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90,% by weight of active compound.
  • the application rates are between 0.1 and 3 kg of active substance or more per hectare. to combat wood-destroying fungi, such as Coniophora tenuna and Polystictus versicolor.
  • the active ingredients are also suitable for the treatment of fruits against mold. They can also be used in conjunction with plastic dispersions to treat wounds against fungal infections.
  • the new active ingredients can also be used as fungicidally active components of oily wood preservatives to protect wood against wood-staining fungi. They are used in such a way that the wood is treated with these agents, for example soaked or painted.
  • agents or the ready-to-use preparations produced therefrom such as solutions, emulsions, suspensions, powders, dusts, pastes or granules, are used in a known manner, for example by spraying, atomizing, dusting, scattering, pickling or pouring.
  • the new agents can also be present together with other active ingredients, e.g. Herbicides, insecticides, growth regulators and fungicides, or also mixed with fertilizers and applied. When mixed with fungicides, the fungicidal activity spectrum is enlarged in many cases.
  • Barley seedlings (Hauters Palatinate summer barley) were sprayed in the single-leaf stage with an aqueous active ingredient solution of various concentrations. 24 hours after the treatment, artificial inoculation with spores of the barley powdery mildew (Erysiphe graminis var. Hordei) took place. The test evaluation was carried out 10 days after the infection.
  • the result of the test shows that the active ingredient 1 when used as 0.0025; 0.005; 0.01 and 0.02 Xige (% by weight) spray liquor produces less leaf damage (1) than the compound N-isotridecyl-2,6-cis-dimethylmorpholine (2) and the compound tridemorph.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

1. Claims for the contracting states : BE, CH, DE, FR, GB, IT, LI, NL, SE A 2,6-trans-dimethylmorpholine derivative of the formula see diagramm : EP0129211,P8,F2 where R is a Cycloalkyl, Cycloalkylalkyl or alkyl radical which can be substituted by one or more C1 -C7 -alkyl radicals, and the total number of carbon atoms in the substituent R is from 7 to 20, and its N-oxides and plant-tolerated addition salts with acids and metal complexes. 1. Claims for the contracting state : AT A fungicide containing a 2,6-trans-dimethylmorpholine derivative of the formula see diagramm : EP0129211,P9,F1 where R is a cycloalkyl, cycloalkylalkyl or alkyl radical which can be substituted by one or more C1 -C7 -alkyl radicals, and the total number of carbon atoms in the substituent R is from 7 to 20, and its N-oxides and plant-tolerated addition salts with acids and metal complexes.

Description

Die vorliegende Erfindung betrifft 2,6-trans-Dimethylmorpholinderivate, diese enthaltende Fungizide und Verfahren zur Bekämpfung von Pilzen.The present invention relates to 2,6-trans-dimethylmorpholine derivatives, fungicides containing them and methods for combating fungi.

Es ist bekannt, N-substituierte 2,6-Dimethylmorpholine, insbesondere das Tridecyl-2,6-dimethylmorpholin (Tridemorph) als Fungizide zu verwenden. (DE 1 164 152). Die bekannten Wirkstoffe bestehen aus Gemischen der Derivate von 2,6-cis- und 2,6-trans-Dimethylmorpholin. Die Pflanzenverträglichkeit dieser Substanzen ist in vielen Fällen nicht ausreichend.It is known to use N-substituted 2,6-dimethylmorpholines, in particular tridecyl-2,6-dimethylmorpholine (tridemorph) as fungicides. (DE 1 164 152). The known active ingredients consist of mixtures of the derivatives of 2,6-cis and 2,6-trans-dimethylmorpholine. The plant tolerance of these substances is in many cases not sufficient.

Es wurde nun gefunden, daß 2,6-trans-Dimethylmorpholinderivate der Formel

Figure imgb0001
in der R einen Cycloalkyl-, Cycloalkylalkyl- oder Alkylrest bedeutet, die durch ein oder mehrere CI-C7-Alkylreste substituiert sein können, und die Zahl der Kohlenstoffatome des Substituenten R insgesamt 7 bis 20 beträgt sowie seine N-Dxide und pflanzenverträglichen Säureadditionssalze und Metallkomplexe wesentlich besser pflanzenverträglich sind als die entsprechenden 2,6-cis-Dimethylmorpholinderivate. Die neuen 2,6-Transdimethylmorpholin-Verbindungen sind besser pflanzenverträglich als die entsprechenden bekannten cis/trans-Gemische (Tridemorph). Dies ist überraschend, weil bei dem bekannten fungiziden Handelsprodukt Fenpropimorph (DE-A 2 656 747) 4-[3-[4-(1,1-Dimethylethyl)-phenyl]-2-methyl]-propyl--2,6(cis)-dimethyl-morpholin das cis-2,6-Dimethylmorpholinderivat Verwendung findet. Es wird also gegenüber dem trans-Derivat bevorzugt. Man müßte daher annehmen, daß auch bei anderen Derivaten jeweils das cis-Derivat das wertvollere der beiden Isomeren ist.It has now been found that 2,6-trans-dimethylmorpholine derivatives of the formula
Figure imgb0001
 in which R represents a cycloalkyl, cycloalkylalkyl or alkyl radical, which can be substituted by one or more C I -C 7 alkyl radicals, and the total number of carbon atoms of the substituent R is 7 to 20 and its N-Dxide and plant-compatible acid addition salts and metal complexes are much better tolerated by plants than the corresponding 2,6-cis-dimethylmorpholine derivatives. The new 2,6-transdimethylmorpholine compounds are better tolerated by plants than the corresponding known cis / trans mixtures (tridemorph). This is surprising because in the known fungicidal commercial product fenpropimorph (DE-A 2 656 747) 4- [3 - [ 4- (1,1-dimethylethyl) phenyl] -2-methyl] propyl - 2,6 ( cis) -dimethyl-morpholine the cis-2,6-dimethylmorpholine derivative is used. It is therefore preferred over the trans derivative. One would therefore have to assume that the cis derivative is also the more valuable of the two isomers in other derivatives.

R bedeutet beispielsweise n-Nonyl, n-Decyl, n-Tridecyl, n-Dodecyl, n-C14H29, n-C15H31, n-C20H411 1,5,9-Trimethyldecyl, 3,7,11-Trimethyldodecyl, 3-Ethyl-1,3,7-trimethyl-octyl, 2-Methyl-tridecyl, 3,5,5-Trimethylhexyl, 4-Ethyl-1-methyl-octyl, 1,4-Diethyl-octyl, 2-Hexyl-hexyl, 1-Methyl--dodecyl, 2-Methyldodecyl, 2-Ethyl-5-cyclohexyl-pentyl, Cyclododecyl--methyl, 4-Ethyl-1-isobutyl-octyl, Cyclooctyl, Cyclononyl, Cyclododecyl. N-Oxide sind z.B. N-n-Tridecyl-2,6-trans-dimethylmorpholin-N-oxid, N-Cyclododecyl-2,6-trana-dimethylmorpholin-N-oxid, ein Gemisch bestehend aus N-Alkyl-2,6-trans-dimethylmorpholln-N-oxiden, wobei der Alkylrest 11 bis 14 Kohlenstoffe enthält.R means, for example, n-nonyl, n-decyl, n-tridecyl, n-dodecyl, nC 14 H 29 , nC 15 H 31 , nC 20H411 1,5,9-trimethyldecyl, 3,7,11-trimethyldodecyl, 3-ethyl -1,3,7-trimethyl-octyl, 2-methyl-tridecyl, 3,5,5-trimethylhexyl, 4-ethyl-1-methyl-octyl, 1,4-diethyl-octyl, 2-hexyl-hexyl, 1 -Methyl - dodecyl, 2-methyldodecyl, 2-ethyl-5-cyclohexylpentyl, cyclododecylmethyl, 4-ethyl-1-isobutyl-octyl, cyclooctyl, cyclononyl, cyclododecyl. N-oxides are, for example, Nn-tridecyl-2,6-trans-dimethylmorpholine- N- oxide, N-cyclododecyl-2,6-tranodimethylmorpholine-N-oxide, a mixture consisting of N-alkyl-2,6-trans -dimethylmorpholln-N-oxides, the alkyl radical containing 11 to 14 carbons.

Säureadditionssalze sind z.B. die Salze mit Salzsäure, HBr, HZS04, H3P04, Essigsäure, Propionsäure, Oxalsäure, n-Dodecylsulfonsäure, n-Dodecylphenylsulfonsäure.Acid addition salts are, for example, the salts with hydrochloric acid, HBr, H Z S0 4 , H 3 P0 4 , acetic acid, propionic acid, oxalic acid, n-dodecylsulfonic acid, n-dodecylphenylsulfonic acid.

Metallkomplexe sind z.B. die Komplexe mit Kupfer, Magnesium, Zink.Metal complexes are e.g. the complexes with copper, magnesium, zinc.

Die aliphatischen oder cycloaliphatischen Reste R können asymmetrische Kohlenstoffe enthalten. Die Wirkstoffe der Formel I können somit in Form verschiedener Enantiomere bzw. Diastereomere vorliegen. Die reinen Enantiomere und Diastereomere sowie ihre Gemische werden von dieser Erfindung umfaßt.The aliphatic or cycloaliphatic radicals R can contain asymmetric carbons. The active compounds of the formula I can therefore be present in the form of various enantiomers or diastereomers. The pure enantiomers and diastereomers and their mixtures are encompassed by this invention.

Die Herstellung der trans-Verbindungen ist wie folgt möglich:

  • 1. Auftrennung der cis-/trans-Gemische durch Dünnschichtchromatographie (n-Hexan/Aceton 9 : 1 - Silicagel).
  • 2. Destillative Trennung der cis/trans-Gemische.
  • 3. Umsetzung von 2,6-trans-Dimethylmorpholin mit einer Verbindung der Formel RX, in der R die im Anspruch 1 genannten Bedeutungen hat und X ein Halogenatom (vorzugsweise Chlor oder Brom) bedeutet.
  • 4. Trennung von 2,6-cis-Dimethylmorpholin und 2,6-trans-Dimethylmorpholin durch Destillation und anschließende Umsetzung von 2,6-trans-Dimethylmorpholin mit einer Verbindung der Formel RX oder Umsetzung mit ROH oder den entsprechenden Ketonen oder Aldehyden und Reduktion.
The trans connections can be produced as follows:
  • 1. Separation of the cis / trans mixtures by thin layer chromatography (n-hexane / acetone 9: 1 - silica gel).
  • 2. Distillative separation of the cis / trans mixtures.
  • 3. Reaction of 2,6-trans-dimethylmorpholine with a compound of the formula RX, in which R has the meanings given in claim 1 and X represents a halogen atom (preferably chlorine or bromine).
  • 4. Separation of 2,6-cis-dimethylmorpholine and 2,6-trans-dimethylmorpholine by distillation and subsequent reaction of 2,6-trans-dimethylmorpholine with a compound of the formula RX or reaction with ROH or the corresponding ketones or aldehydes and reduction .

Vorschrift 1Regulation 1 Herstellung von Iso-Tridecylchlorid (A)Production of iso-tridecyl chloride (A)

Zu 322 g SOC1 2 wurden 450 g Iso-Tridecanol (mit Isotridecanol bezeichnen wir ein handelsübliches Gemisch verschiedener homologer C11-C14-Alkohole, das 60 bis 70 % Tridecylalkohol enthält) zugetropft. Man rührte über Nacht, erwärmte 2 h auf 140°C, destillierte das Rohprodukt und erhielt 433 g farbloses öl, Sdp. 84 bis 86°C/0,3 bar.450 g of isotridecanol (with isotridecanol we refer to a commercially available mixture of different homologous C 11 -C 14 alcohols which contains 60 to 70% tridecyl alcohol) were added dropwise to 322 g SOC1 2 . The mixture was stirred overnight, heated to 140 ° C. for 2 h, the crude product was distilled and 433 g of colorless oil were obtained, bp 84 to 86 ° C./0.3 bar.

Beispiel 1example 1 Herstellung von N-Iso-Tridecyl-2,6-trans-dimethylmorpholin (Wirkstoff Nr. 1)Production of N-iso-tridecyl-2,6-trans-dimethylmorpholine (active ingredient No. 1)

30 g A und 48 g 2,6-trans-Dimethylmorpholin wurden 8 h auf 150° erwärmt. Das Rohprodukt wurde in CH2C12 gelöst, mit verdünnter wäßriger NaOH und anschließend mehrfach mit Wasser gewaschen. Man trocknete über Na2S04, engte ein, destillierte und erhielt 16 g farbloses öl, Sdp. 122°C/0,2 mbar.30 g of A and 48 g of 2,6-trans-dimethylmorpholine were heated to 150 ° for 8 h. The crude product was dissolved in CH 2 C1 2 , washed with dilute aqueous NaOH and then washed several times with water. It was dried over Na 2 SO 4 , concentrated, distilled and 16 g of colorless oil, bp 122 ° C / 0.2 mbar.

Beispiel 2Example 2 Herstellung von N-Cyclododecyl-2,6-trans-dimethylmorpholin (Wirkstoff Nr. 23)Production of N-cyclododecyl-2,6-trans-dimethylmorpholine (active ingredient no.23)

130 g Cyclododecanon, 138 g 2,6-trans-Dimethylmorpholin und 1 g p-Toluolsulfonsäure wurden 15 h am Wasserabscheider zum Rückfluß erwärmt. Das so erhaltene Rohprodukt wurde nach Abkühlen mit Wasser gewaschen, über MgS04 getrocknet, eingeengt und destilliert. Nach nichtumgesetzten Vorprodukten destillierten 64 g (140 bis 145°C/0,3 mbar) gelbliches öl = N-Cyclododece- nyl-2,6-trans-dimethylmorpholin (B).130 g of cyclododecanone, 138 g of 2,6-trans-dimethylmorpholine and 1 g of p-toluenesulfonic acid were heated to reflux on a water separator for 15 h. The crude product thus obtained was washed with water after cooling, dried over MgSO 4 , concentrated and distilled. After unreacted preliminary products, 64 g (140 to 145 ° C / 0.3 mbar) of yellowish oil = N-cyclododecenyl-2,6-trans-dimethylmorpholine (B) distilled.

Das erhaltene Enamin (B) wurde in Essigester gelöst und nach Zugabe von 5 g Pd/C-Kontakt (10 Gew.% Pd) bei 60 bis 70°C/100 bar hydriert. Danach engte man ein und destillierte. Man erhielt 45 g farbloses öl, Sdp. 136 bis 138°C/0,2 mbar.The enamine (B) obtained was dissolved in ethyl acetate and, after the addition of 5 g of Pd / C contact (10% by weight of Pd), was hydrogenated at 60 to 70 ° C./100 bar. Then it was concentrated and distilled. 45 g of colorless oil, b.p. 136 to 138 ° C / 0.2 mbar were obtained.

In entsprechender Weise wurden die folgenden mit physikalischen Daten gekennzeichneten Verbindungen hergestellt:

Figure imgb0002
The following connections marked with physical data were correspondingly established:
Figure imgb0002

Die neuen Verbindungen und ihre Salze, Metallkomplexverbindungen und Oxide zeichnen sich durch eine hervorragende Wirksamkeit gegen ein breites Spektrum von pflanzenpathogenen Pilzen, insbesondere aus der Klasse der Ascomyceten und Basidiomyceten, aus. Sie sind zum Teil systemisch wirksam und können als Blatt- und Bodenfungizide eingesetzt werden. Ferner können sie auch im Materialschutz verwendet werden.The new compounds and their salts, metal complex compounds and oxides are distinguished by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes and Basidiomycetes. Some of them are systemically effective and can be used as foliar and soil fungicides. They can also be used in material protection.

Besonders interessant sind die fungiziden Verbindungen für die Bekämpfung einer Vielzahl von Pilzen an verschiedenen Kulturpflanzen oder ihren Samen, insbesondere Weizen, Roggen, Gerste, Hafer, Reis, Mais, Baumwolle, Soja, Kaffe, Bananen, Zuckerrohr, Obst und Zierpflanzen im Gartenbau, sowie Gemüse - wie Gurken, Bohnen und Kürbisgewächse -.The fungicidal compounds are particularly interesting for controlling a large number of fungi on various crop plants or their seeds, in particular wheat, rye, barley, oats, rice, corn, cotton, soybeans, coffee, bananas, sugar cane, fruit and ornamental plants in horticulture, and Vegetables - such as cucumbers, beans and pumpkin plants -.

Die neuen Verbindungen sind insbesondere geeignet zur Bekämpfung folgender Pflanzenkrankheiten:

  • Erysiphe graminis (echter Mehltau) in Getreide,
  • Erysiphe cichoriacearum (echter Methltau) an Kürbisgewächsen,
  • Podosphaera leucotricha an Äpfeln,
  • Uncinula necator an Reben,
  • Erysiphe polygoni an Bohnen,
  • Sphaerotheca pannosa an Rosen,
  • Puccinia-Arten an Getreide,
  • Mycosphaerella musicola an Bananen,
  • Corticium salmonicolor an Hevea,
  • Ganoderma pseudoferreum an Hevea und
  • Exobasidium vexans an Tee.
The new compounds are particularly suitable for controlling the following plant diseases:
  • Erysiphe graminis (powdery mildew) in cereals,
  • Erysiphe cichoriacearum (real methau) on pumpkin plants,
  • Podosphaera leucotricha on apples,
  • Uncinula necator on vines,
  • Erysiphe polygoni on beans,
  • Sphaerotheca pannosa on roses,
  • Puccinia species on cereals,
  • Mycosphaerella musicola on bananas,
  • Corticium salmonicolor on Hevea,
  • Ganoderma pseudoferreum on Hevea and
  • Exobasidium vexans on tea.

Die Verbindungen werden angewendet, indem man die Pflanzen mit den Wirkstoffen besprüht oder bestäubt oder die Samen der Pflanzen mit den Wirkstoffen behandelt. Die Anwendung erfolgt vor oder nach der Infektion der Pflanzen oder Samen durch die Pilze.The compounds are applied by spraying or dusting the plants with the active compounds or by treating the seeds of the plants with the active compounds. It is used before or after the plants or seeds are infected by the fungi.

Die neuen Substanzen können in die üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Stäube, Pulver, Pasten und Granulate. Die Anwendungsformen richten sich ganz nach den Verwendungszwecken; sie sollen in jedem Fall eine feine und gleichmäßige Verteilung der wirksamen Substanz gewährleisten. Die Formulierungen werden in bekannter Weise hergestellt, z.B. durch Verstrecken des Wirkstoffs mit Lösungsmitteln und/oder Trägerstoffen, gegebenenfalls unter Verwendung von Emulgiermitteln und Dispergiermitteln, wobei im Falle der Benutzung von Wasser als Verdünnungsmittel auch andere organische Lösungsmittel als Hilfslösungsmittel verwendet werden können. Als Hilfsstoffe kommen dafür im wesentlichen in Frage: Lösungsmittel wie Aromaten (z.B. Xylol, Benzol), chlorierte Aromaten (z.B. Chlorbenzole), Paraffine (z.B. Erdölfraktionen), Alkohole (z.B. Methanol, Butanol), Amine (z.B. Ethanolamin, Dimethylformamid) und Wasser; Trägerstoffe wie natürliche Gesteinsmehle, z.B. Kaoline, Tonerden, Talkum, Kreide und synthetische Gesteinsmehle (z.B. hochdisperse Kieselsäure, Silikate); Emulgiermittel, wie nichtionogene und anionische Emulgatoren (z.B. Polyoxyethylen-Fettalkohol-Ether, Alkylsulfonate und Arylsulfonate) und Dispergiermittel, wie Lignin, Sulfitablaugen und Methylcellulose.The new substances can be converted into the usual formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes; in any case, they should ensure a fine and uniform distribution of the active substance. The formulations are prepared in a known manner, for example by extending the active ingredient with solvents and / or carriers, if appropriate using emulsifiers and dispersants, and if water is used as the diluent, other organic solvents can also be used as auxiliary solvents. The following are essentially suitable as auxiliaries: solvents such as aromatics (eg xylene, benzene), chlorinated aromatics (eg chlorobenzenes), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol), amines (eg ethanolamine, dimethylformamide) and water; Carriers such as natural stone powder, for example kaolins, clays, talc, chalk and synthetic stone powder (for example highly disperse silica, silicates); Emulsifiers, such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ether, Alkyl sulfonates and aryl sulfonates) and dispersants such as lignin, sulfite waste liquors and methyl cellulose.

Die fungiziden Mittel enthalten im allgemeinen zwischen 0,1 und 95, vorzugsweise zwischen 0,5 und 90 Gew.X Wirkstoff.The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90,% by weight of active compound.

Die Aufwandmengen liegen je nach Art des gewünschten Effektes zwischen 0,1 und 3 kg Wirkstoff oder mehr je ha. Die neuen Verbindungen können auch im Materialschutz u.a. zur Bekämpfung holzzerstörender Pilze, wie Coniophora puteana und Polystictus versicolor eingesetzt werden. Die Wirkstoffe eignen sich auch zur Behandlung von Früchten gegen Schimmelpilzbefall. Ferner können sie in Verbindung mit Kunststoffdispersionen zu Wundbehandlungen gegen pilzliche Infektionen verwendet werden. Die neuen Wirkstoffe können auch als fungizid wirksame Bestandteile öliger Holzschutzmittel zum Schutz von Holz gegen holzverfärbende Pilze eingesetzt werden. Die Anwendung erfolgt in der Weise, daß man das Holz mit diesen Mitteln behandelt, beispielsweise tränkt oder anstreicht.Depending on the type of effect desired, the application rates are between 0.1 and 3 kg of active substance or more per hectare. to combat wood-destroying fungi, such as Coniophora puteana and Polystictus versicolor. The active ingredients are also suitable for the treatment of fruits against mold. They can also be used in conjunction with plastic dispersions to treat wounds against fungal infections. The new active ingredients can also be used as fungicidally active components of oily wood preservatives to protect wood against wood-staining fungi. They are used in such a way that the wood is treated with these agents, for example soaked or painted.

Die Mittel bzw. die daraus hergestellten gebrauchsfertigen Zubereitungen, wie Lösungen, Emulsionen, Suspensionen, Pulver, Stäube, Pasten oder Granulate werden in bekannter Weise angewendet, beispielsweise durch Versprühen, Vernebeln, Verstäuben, Verstreuen, Beizen oder Gießen.The agents or the ready-to-use preparations produced therefrom, such as solutions, emulsions, suspensions, powders, dusts, pastes or granules, are used in a known manner, for example by spraying, atomizing, dusting, scattering, pickling or pouring.

Beispiele für solche Zubereitungen sind:

  • I. Man vermischt 90 Gewichtsteile der Verbindung des Beispiels 1 mit 10 Gewichtsteilen N-Methyl-alpha-pyrrolidon und erhält eine Lösung, die zur Anwendung in Form kleinster Tropfen geeignet ist.
  • II. 20 Gewichtsteile der Verbindung des Beispiels 2 werden in einer Mischung gelöst, die aus 80 Gewichtsteilen Xylol, 10 Gewichtsteilen des Anlagerungsproduktes von 8 bis 10 Mol Ethylenoxid an 1 Mol 01- säure-N-monoethanolamid, 5 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsäure und 5 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht. Durch Ausgießen und feines Verteilen der Lösung in Wasser erhält man eine wäßrige Dispersion.
  • III. 20 Gewichtsteile der Verbindung 4 werden in einer Mischung gelöst, die aus 40 Gewichtsteilen Cyclohexanon, 30 Gewichtsteilen Isobutanol, 20 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in Wasser erhält man eine wäßrige Dispersion.
  • IV. 20 Gewichtsteile der Verbindung des Beispiels 1 werden in einer Mischung gelöst, die aus 25 Gewichtsteilen Cyclohexanol, 65 Gewichtsteilen einer Mineralölfraktion vom Siedepunkt 210 bis 280°C und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in Wasser erhält man eine wäßrige Dispersion.
  • V. 20 Gewichtsteile der Verbindung des Beispiels 2 werden mit 3 Gewichtsteilen des Natriumsalzes der Diisobutylnaphthalin-alpha-sulfonsäure, 17 Gewichtsteilen des Natriumsalzes einer Ligninsulfonsäure aus einer Sulfitlauge und 60 Gewichtsteilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermahlen. Durch feines Verteilen der Mischung in Wasser erhält man eine Spritzbrühe.
  • VI. 3 Gewichtsteile der Verbindung 4 werden mit 97 Gewichtsteilen feinteiligem Kaolin innig vermischt. Man erhält auf diese Weise ein Stäubemittel, das 3 Gew.X des Wirkstoffs enthält.
  • VII. 30 Gewichtsteile der Verbindung des Beispiels 2 werden mit einer Mischung aus 92 Gewichtsteilen pulverförmigem Kieselsäuregel und 8 Gewichtsteilen Paraffinöl, das auf die Oberfläche dieses Kieselsäuregels gesprüht wurde, innig vermischt. Man erhält auf diese Weise eine Aufbereitung des Wirkstoffs mit guter Haftfähigkeit.
  • VIII. 40 Gewichtsteile der Verbindung des Beispiels 1 werden mit 10 Teilen Natriumsalz eines Phenolsulfonsäure-harnstoff-formaldehyd-Kondensates, 2 Teilen Kieselgel und 48 Teilen Wasser innig vermischt. Man erhält eine stabile wäßrige Dispersion. Durch Verdünnen mit Wasser erhält man eine verdünnte wäßrige Dispersion.
  • IX. 20 Teile der Verbindung des Beispiels 4 werden mit 2 Teilen Calciumsalz der Dodecylbenzolsulfonsäure, 8 Teilen Fettalkohol-polyglykolether, 2 Teilen Natriumsalz eines Phenolsulfonsäure-harnstoff-formaldehyd-Kondensats und 68 Teilen eines paraffinischen Mineralöls innig vermischt. Man erhält eine stabile ölige Dispersion.
Examples of such preparations are:
  • I. 90 parts by weight of the compound of Example 1 are mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone and a solution is obtained which is suitable for use in the form of minute drops.
  • II. 20 parts by weight of the compound of Example 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of 01-acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.
  • III. 20 parts by weight of compound 4 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into water and finely distributing it therein gives an aqueous dispersion.
  • IV. 20 parts by weight of the compound of Example 1 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into water and finely distributing it therein gives an aqueous dispersion.
  • V. 20 parts by weight of the compound of Example 2 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite solution and 60 parts by weight of powdered silica gel and ground in a hammer mill. A spray liquor is obtained by finely distributing the mixture in water.
  • VI. 3 parts by weight of compound 4 are intimately mixed with 97 parts by weight of finely divided kaolin. In this way a dust is obtained which contains 3% by weight of the active ingredient.
  • VII. 30 parts by weight of the compound of Example 2 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, a preparation of the active ingredient with good adhesiveness is obtained.
  • VIII. 40 parts by weight of the compound of Example 1 are intimately mixed with 10 parts of sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with water gives a dilute aqueous dispersion.
  • IX. 20 parts of the compound of Example 4 are intimately mixed with 2 parts of calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

Die neuen Mittel können in diesen Anwendungsformen auch zusammen mit anderen Wirkstoffen vorliegen, wie z.B. Herbiziden, Insektiziden, Wachstumsregulatoren und Fungiziden, oder auch mit Düngemitteln vermischt und ausgebracht werden. Beim Vermischen mit Fungiziden erhält man dabei in vielen Fällen eine Vergrößerung des fungiziden Wirkungsspektrums.In these forms of use, the new agents can also be present together with other active ingredients, e.g. Herbicides, insecticides, growth regulators and fungicides, or also mixed with fertilizers and applied. When mixed with fungicides, the fungicidal activity spectrum is enlarged in many cases.

Die folgende Liste von Fungiziden, mit denen die erfindungsgemäßen Verbindungen kombiniert werden können, soll die Kombinationsmöglichkeiten erläutern, nicht aber einschränken.The following list of fungicides with which the compounds according to the invention can be combined is intended to explain, but not to limit, the possible combinations.

Fungizide, die mit den neuen Verbindungen kombiniert werden können, sind beispielsweise:

  • Schwefel,
  • Dithiocarbamate und deren Derivate, wie Ferridimethyldithiocarbamat, Zinkdimethyldithiocarbamat, Manganethylenbisdithiocarbamat, Mangan-Zink-ethylendiamin-bis-dithiocarbamat oder Zinkethylenbisdithiocarbamat, Tetramethylthiuramdisulfide,
  • Ammoniak-Komplex von Zink-(N,N-ethylen-bis-dithiocarbamat) und N,N'-Polyethylen-bis-(thiocarbamoyl)-disulfid,
  • Zink-(N,N'-propylen-bis-dithiocarbamat),
  • Ammoniak-Komplex von Zink-(N,N'-propylen-bis-dithiocarbamat) und N,N'-Propylen-bis(thiocarbamoyl)-disulfid;
  • Nitroderivate, wie
  • Dinitro-(l-methylheptyl)-phenylcrotonat,
  • 2-sec.-Butyl-4,6-dinitrophenyl-3,3-dimethylacrylat,
  • 2-sec.-Butyl-4,6-dinitrophenyl-isopropylcarbonat;
  • heterocyclische Substanzen, wie
  • N-Trichlormethylthio-tetrahydrophthalimid,
  • N-(1,1,2,2-Tetrachlorethylthio)-tetrahydrophthalimid, N-Trichlormethylthio-phthalimid,
  • 2-Heptadecyl-2-imidazolin-acetat,
  • 2,4-Dichlor-6-(o-chloranilino)-s-triazin,
  • 0,0-Diethyl-phthalimidophosphonothioat,
  • 5-Amino-1-(bis-(dimethylamino)-phosphinyl)-3-ghenyl-1,2,4-triazol, 5-Ethoxy-3-trichlormethyl-1,2,4-thiadiazol,
  • 2,3-Dicyano-1,4-dithioanthrachinon,
  • 2-Thio-1,3-dithio-(4,5-b)-chinoxalin,
  • 1-(Butylcarbamoyl)-2-benzimidazol-carbaminsäuremethylester, 2-Methoxycarbonylamino-benzimidazol,
  • 2-Thodanmethylthio-benzthiazol,
  • 4-(2-Chlorphenylhydrazono)-3-methyl-5-isoxazolon,
  • Pyridin-2-thiol-l-oxid,
  • 8-Hydroxychinolin bzw. dessen Kupfersalz,
  • 2,3-Dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxid, 2,3-Dihydro-5-carboxanilido-6-methyl-1,4-oxathiin,
  • 2-(Furyl)-benzimidazol,
  • Piperazin-1,4-diyl-bis-(1-(2,2,2-trichlor-ethyl)-formamid), 2-(Thiazolyl-(4))-benzimidazol,
  • 5-Butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidin, Bis-(p-Chlorphenyl)-pyridinmethanol,
  • 1,2-Bis-(3-ethoxycarbonyl-2-thioureido)-benzol,
  • 1,2-Bis-(3-methoxycarbonyl-2-thioureido)-benzol
  • und weitere Substanzen, wie
  • Dodecylguanidinacetat,
  • 3-(3-(3,5-Dimethyl-2-oxycyclohexyl)-2-hydroxyethyl)-glutaramid, Hexachlorbenzol,
  • N-Dichlorfluormethylthio-N',N'-dimethyl-N-phenyl-schwefelsäurediamid, 2,5-Dimethyl-furan-3-carbonsäureanilid,
  • 2,5-Dimethyl-furan-3-carbonsäure-cyclohexylamid,
  • 2-Cyan-N-(ethylaminocarbonyl)-2-(methoxyimino)-acetamid, 2-Methyl-benzoesäure-anilid,
  • 2-Iod-benzoesäure-anilid,
  • 1-(3,4-Dichloranilino)-1-formylamino-2,2,2-trichlorethan,
  • DL-Methyl-N-2,6-dimethyl-phenyl)-N-furoyl(2)-alaninat,
  • DL-N-(2,6-Dimethyl-phenyl)-N-(2'-methoxyacetyl)-alanin-methylester,
  • 5-Nitro-isophthalsäure-di-isopropylester,
  • 1-(1',2',4'-Triazolyl-1')-4'-chlorphenoxy)-3,3-dimethylbutan-2-on,
  • 1-(1',2',4'-Triazolyl-1')-1-(4'-chlorphenoxy)-3,3-dimethylbutan-2-ol,
  • N-(2,6-Dimethylphenyl)-N-chloracetyl-D,L-2-aminobutyrolacton,
  • N-(n-Propyl)-N-(2,4,6-trichlorphenoxyethyl)-N'-imidazolylharnstoff.
Fungicides that can be combined with the new compounds include:
  • Sulfur,
  • Dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylene bisdithiocarbamate, manganese zinc ethylenediamine bisdithiocarbamate or zinc ethylene bisdithiocarbamate, tetramethylthiuram disulfide,
  • Ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate) and N, N'-polyethylene-bis- (thiocarbamoyl) disulfide,
  • Zinc (N, N'-propylene-bis-dithiocarbamate),
  • Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate) and N, N'-propylene-bis (thiocarbamoyl) disulfide;
  • Nitroderivatives, such as
  • Dinitro- (l-methylheptyl) phenyl crotonate,
  • 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate,
  • 2-sec-butyl-4,6-dinitrophenyl-isopropyl carbonate;
  • heterocyclic substances, such as
  • N-trichloromethylthio-tetrahydrophthalimide,
  • N- (1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-phthalimide,
  • 2-heptadecyl-2-imidazoline acetate,
  • 2,4-dichloro-6- (o-chloroanilino) -s-triazine,
  • 0,0-diethyl phthalimidophosphonothioate,
  • 5-amino-1- (bis- (dimethylamino) phosphinyl) -3-ghenyl-1,2,4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole,
  • 2,3-dicyano-1,4-dithioanthraquinone,
  • 2-thio-1,3-dithio- (4,5-b) -quinoxaline,
  • 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole,
  • 2-thodanmethylthio-benzothiazole,
  • 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone,
  • Pyridine-2-thiol-l-oxide,
  • 8-hydroxyquinoline or its copper salt,
  • 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,
  • 2- (furyl) benzimidazole,
  • Piperazin-1,4-diyl-bis- (1- (2,2,2-trichloro-ethyl) -formamide), 2- (thiazolyl- (4)) - benzimidazole,
  • 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis (p-chlorophenyl) pyridine methanol,
  • 1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene,
  • 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene
  • and other substances, such as
  • Dodecylguanidine acetate,
  • 3- (3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl) glutaramide, hexachlorobenzene,
  • N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenyl-sulfuric acid diamide, 2,5-dimethyl-furan-3-carboxylic acid anilide,
  • 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide,
  • 2-cyano-N- (ethylaminocarbonyl) -2- (methoxyimino) acetamide, 2-methylbenzoic acid anilide,
  • 2-iodo-benzoic acid anilide,
  • 1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane,
  • DL-methyl-N-2,6-dimethyl-phenyl) -N-furoyl (2) alaninate,
  • DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester,
  • 5-nitro-isophthalic acid di-isopropyl ester,
  • 1- (1 ', 2', 4'-triazolyl-1 ') - 4'-chlorophenoxy) -3,3-dimethylbutan-2-one,
  • 1- (1 ', 2', 4'-triazolyl-1 ') - 1- (4'-chlorophenoxy) -3,3-dimethylbutan-2-ol,
  • N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone,
  • N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazolylurea.

Der folgende Versuch zeigt die biologische Wirksamkeit gegen echten Mehltau (Erysiphe graminis var. hordei) und insbesondere die Pflanzenverträglichkeit der neuen N-substituierten 2,6-trans-Dimethylmorpholine.The following experiment shows the biological effectiveness against powdery mildew (Erysiphe graminis var. Hordei) and in particular the plant tolerance of the new N-substituted 2,6-trans-dimethylmorpholines.

Versuchattempt

Gerstenkeimlinge (Hauters Pfälzer Sommergerste) wurden im Einblattstadium mit wäßriger Wirkstofflösung verschiedener Konzentration besprüht. 24 Stunden nach der Behandlung erfolgte die künstliche Beimpfung mit Sporen des Gerstenmehltaus (Erysiphe graminis var. hordei). Die Versuchsauswertung wurde 10 Tage nach der Infektion vorgenommen.Barley seedlings (Hauters Palatinate summer barley) were sprayed in the single-leaf stage with an aqueous active ingredient solution of various concentrations. 24 hours after the treatment, artificial inoculation with spores of the barley powdery mildew (Erysiphe graminis var. Hordei) took place. The test evaluation was carried out 10 days after the infection.

Das Ergebnis des Versuches zeigt, daß der Wirkstoff 1 bei der Anwendung als 0,0025; 0,005; 0,01 und 0,02 Xige (Gew.%) Spritzbrühe geringere Blattschäden (1) erzeugt als die Verbindung N-Isotridecyl-2,6-cis-dimethylmorpholin (2) und die Verbindung Tridemorph.The result of the test shows that the active ingredient 1 when used as 0.0025; 0.005; 0.01 and 0.02 Xige (% by weight) spray liquor produces less leaf damage (1) than the compound N-isotridecyl-2,6-cis-dimethylmorpholine (2) and the compound tridemorph.

Claims (7)

1. 2,6-trans-Dimethylmorpholinderivat der Formel
Figure imgb0003
in der R einen Cycloalkyl-, Cycloalkylalkyl- oder Alkylrest bedeutet, die durch ein oder mehrere C1-C7-Alkylreste substituiert sein können, und die Zahl der Kohlenstoffatome des Substituenten R insgesamt 7 bis 20 beträgt sowie seine N-Oxide und pflanzenverträglichen Säureadditionssalze und Metallkomplexe.1. 2,6-trans-Dimethylmorpholinderivat of the formula
Figure imgb0003
 in which R is a cycloalkyl, cycloalkylalkyl or alkyl radical which may be substituted by one or more C 1 -C 7 -alkyl radicals, and the number of carbon atoms of the substituent R is 7 to 20 in total, and its N-oxides and plant-compatible acid addition salts and metal complexes. 2. Fungizid enthaltend eine Verbindung der Formel I gemäß Anspruch 1.2. A fungicide containing a compound of the formula I according to claim 1. 3. Fungizid enthaltend eine Verbindung der Formel I gemäß Anspruch 1 und einen festen oder flüssigen Trägerstoff.3. A fungicide containing a compound of the formula I according to claim 1 and a solid or liquid carrier. 4. Verfahren zur Bekämpfung von Pilzen dadurch gekennzeichnet, daß man eine fungizid wirksame Menge einer Verbindung der Formel I gemäß Anspruch 1 auf durch Pilzbefall bedrohte Materialien, Flächen, Pflanzen oder Saatgüter oder auf die Pilze einwirken läßt.4. A method for combating fungi, characterized in that a fungicidally effective amount of a compound of formula I according to claim 1 is allowed to act on fungal infection endangered materials, areas, plants or seeds or on the fungi. 5. Verfahren zur Herstellung von 2,6-trans-Dimethylmorpholinen, wie im Anspruch 1 definiert, dadurch gekennzeichnet, daß man eine Verbindung der Formel RX, in der R die obengenannten Bedeutungen hat und X ein Halogenatom bedeutet, mit 2,6-trans-Dimethylmorpholin umsetzt.5. A process for the preparation of 2,6-trans-Dimethylmorpholinen as defined in claim 1, characterized in that a compound of the formula RX in which R has the abovementioned meanings and X is a halogen atom, with 2,6-trans Dimethylmorpholine. 6. 2,6-trans-Dimethylmorpholinderivat gemäß Anspruch 1 nämlich N-n-Tridecyl-2,6-trans-dimethyl-morpholin, N-n-Dodecyl-2,6-trans-dimethyl-morpholin, N-Cyclododecyl-2,6-trans-dimethyl-morpholin oder ein Gemisch bestehend aus N-Alkyl-2,6-trans-dimethyl-morpholinen, wobei der Alkylrest gegebenenfalls verzweigt ist und jeweils 11 bis 14 Kohlenstoffatome enthält.6. 2,6-trans-Dimethylmorpholinderivat according to claim 1 namely Nn-tridecyl-2,6-trans-dimethyl-morpholine, Nn-dodecyl-2,6-trans-dimethyl-morpholine, N-cyclododecyl-2,6-trans -dimethyl-morpholine or a mixture consisting of N-alkyl-2,6-trans-dimethyl-morpholines, wherein the alkyl radical is optionally branched and contains in each case 11 to 14 carbon atoms. 7. Fungizides Mittel enthaltend ein 2,6-trans-Dimethylmorpholinderivat gemäß Anspruch 1, nämlich N-n-Tridecyl-2,6-trans-dimethyl-morpholin, N-n-Dodecyl-2,6-trans-dimethyl-morpholin, N-Cyclododecyl-2,6-trans--dimethyl-morpholin oder ein Gemisch bestehend aus N-Alkyl-2,6--trans-dimethyl-morpholinen, wobei der Alkylrest gegebenenfalls verzweigt ist und jeweils 11 bis 14 Kohlenstoffatome enthält.7. A fungicidal composition containing a 2,6-trans-Dimethylmorpholinderivat according to claim 1, namely Nn-tridecyl-2,6-trans-dimethyl-morpholine, Nn-dodecyl-2,6-trans-dimethyl-morpholine, N-cyclododecyl 2,6-trans-dimethyl-morpholine or a mixture consisting of N-alkyl-2,6-trans-dimethyl-morpholines, wherein the alkyl radical is optionally branched and contains in each case 11 to 14 carbon atoms.
EP84106796A 1983-06-16 1984-06-14 2,6-trans-dimethyl morpholine derivatives, fungicides containing them and methods of combating fungi Expired EP0129211B1 (en)

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AT84106796T ATE25379T1 (en) 1983-06-16 1984-06-14 2,6-TRANS-DIMETHYLMORPHOLINE DERIVATIVES AND CONTAINING FUNGICIDES AND METHODS FOR CONTROLLING FUNGI.
MYPI87000856A MY101892A (en) 1983-06-16 1987-06-20 2,6-trans-dimethylmorpholine derivatives, fungicides containing these compounds, and methods of controlling fungi

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DE3321712 1983-06-16
DE3321712A DE3321712A1 (en) 1983-06-16 1983-06-16 2,6-TRANS-DIMETHYLMORPHOLINE DERIVATIVES AND FUNGICIDES CONTAINING THEM AND METHOD FOR CONTROLLING FUNGI

Publications (2)

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EP0129211A1 true EP0129211A1 (en) 1984-12-27
EP0129211B1 EP0129211B1 (en) 1987-02-04

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EP84106796A Expired EP0129211B1 (en) 1983-06-16 1984-06-14 2,6-trans-dimethyl morpholine derivatives, fungicides containing them and methods of combating fungi

Country Status (8)

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EP (1) EP0129211B1 (en)
AT (1) ATE25379T1 (en)
CS (1) CS249138B2 (en)
DD (1) DD215931A5 (en)
DE (2) DE3321712A1 (en)
DK (1) DK164667C (en)
MY (1) MY101892A (en)
PH (1) PH20933A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0193890A1 (en) * 1985-03-02 1986-09-10 BASF Aktiengesellschaft Wood preservative
EP0223095A1 (en) * 1985-11-07 1987-05-27 BASF Aktiengesellschaft Wood protection agent
EP0253501A2 (en) * 1986-07-16 1988-01-20 Imperial Chemical Industries Plc N-disubstituted cycloalkylmethyl amines useful as fungicides
US5021459A (en) * 1988-11-24 1991-06-04 Dr. Wolman Gmbh Wood preservatives
EP0193065B1 (en) * 1985-02-22 1995-08-23 BASF Aktiengesellschaft Morpholine derivatives, processes for their production and their use as fungicides
WO2002074755A1 (en) * 2001-03-16 2002-09-26 Basf Aktiengesellschaft Method of producing n-substituted 2,6-dialkyl morpholines

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD256072A1 (en) * 1985-03-04 1988-04-27 Adl Der Ddr Inst Fuer Pflanzen FUNGICIDES AND PLANT GROWTH-REGULATING AGENTS
FI874121A (en) * 1986-09-24 1988-03-25 Sumitomo Chemical Co HETEROCYCLISKA FOERENINGAR, OCH DERAS FRAMSTAELLNING OCH ANVAENDNING.
DE3643009A1 (en) * 1986-12-17 1988-06-30 Basf Ag FUNGICIDAL CYCLOHEXYLAMINE

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1164152B (en) * 1961-02-22 1964-02-27 Basf Ag Fungicides
DE1214471B (en) * 1965-01-16 1966-04-14 Basf Ag Fungicide for crop protection
DE2461513A1 (en) * 1974-12-27 1976-07-08 Basf Ag MORPHOLINE DERIVATIVES
DE2752135A1 (en) * 1976-11-22 1978-05-24 Hoffmann La Roche HETEROCYCLIC COMPOUNDS
DE2700680A1 (en) * 1977-01-08 1978-07-20 Basf Ag (N)-Substd. morpholinium salt prodn. - by acid cyclisation of bis:hydroxyalkyl-ammonium salts
EP0019764A1 (en) * 1979-05-25 1980-12-10 BASF Aktiengesellschaft Trans-3-(4'-tert.-butyl-cyclohexyl-1')-2-methyl-1-(3'-methylpiperidino, 3',5'-dimethylpiperidino and 2', 6'-dimethylmorpholino) propane, process for their pure preparation, antimycotic agents containing them and their utilisation

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2656747C2 (en) * 1976-12-15 1984-07-05 Basf Ag, 6700 Ludwigshafen Morpholine derivatives

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1164152B (en) * 1961-02-22 1964-02-27 Basf Ag Fungicides
DE1173722B (en) * 1961-02-22 1964-07-09 Basf Ag Fungicides
DE1198125B (en) * 1961-02-22 1965-08-05 Basf Ag Fungicides
DE1214471B (en) * 1965-01-16 1966-04-14 Basf Ag Fungicide for crop protection
DE2461513A1 (en) * 1974-12-27 1976-07-08 Basf Ag MORPHOLINE DERIVATIVES
DE2752135A1 (en) * 1976-11-22 1978-05-24 Hoffmann La Roche HETEROCYCLIC COMPOUNDS
DE2700680A1 (en) * 1977-01-08 1978-07-20 Basf Ag (N)-Substd. morpholinium salt prodn. - by acid cyclisation of bis:hydroxyalkyl-ammonium salts
EP0019764A1 (en) * 1979-05-25 1980-12-10 BASF Aktiengesellschaft Trans-3-(4'-tert.-butyl-cyclohexyl-1')-2-methyl-1-(3'-methylpiperidino, 3',5'-dimethylpiperidino and 2', 6'-dimethylmorpholino) propane, process for their pure preparation, antimycotic agents containing them and their utilisation

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0193065B1 (en) * 1985-02-22 1995-08-23 BASF Aktiengesellschaft Morpholine derivatives, processes for their production and their use as fungicides
EP0193890A1 (en) * 1985-03-02 1986-09-10 BASF Aktiengesellschaft Wood preservative
EP0223095A1 (en) * 1985-11-07 1987-05-27 BASF Aktiengesellschaft Wood protection agent
EP0253501A2 (en) * 1986-07-16 1988-01-20 Imperial Chemical Industries Plc N-disubstituted cycloalkylmethyl amines useful as fungicides
EP0253501A3 (en) * 1986-07-16 1990-04-04 Imperial Chemical Industries Plc N-disubstituted cycloalkylmethyl amines useful as fungicides
US5021459A (en) * 1988-11-24 1991-06-04 Dr. Wolman Gmbh Wood preservatives
WO2002074755A1 (en) * 2001-03-16 2002-09-26 Basf Aktiengesellschaft Method of producing n-substituted 2,6-dialkyl morpholines

Also Published As

Publication number Publication date
DD215931A5 (en) 1984-11-28
EP0129211B1 (en) 1987-02-04
DE3321712A1 (en) 1984-12-20
ATE25379T1 (en) 1987-02-15
DK293484D0 (en) 1984-06-15
CS249138B2 (en) 1987-03-12
DE3462332D1 (en) 1987-03-12
PH20933A (en) 1987-06-05
DK293484A (en) 1984-12-17
DK164667C (en) 1992-12-21
DK164667B (en) 1992-07-27
MY101892A (en) 1992-02-15

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